US11031566B2 - Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell - Google Patents

Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell Download PDF

Info

Publication number
US11031566B2
US11031566B2 US16/319,236 US201716319236A US11031566B2 US 11031566 B2 US11031566 B2 US 11031566B2 US 201716319236 A US201716319236 A US 201716319236A US 11031566 B2 US11031566 B2 US 11031566B2
Authority
US
United States
Prior art keywords
layer
precursor
solar cell
organic
inorganic hybrid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active, expires
Application number
US16/319,236
Other versions
US20190280229A1 (en
Inventor
Sang Jun Park
Seiyong KIM
Jong Seok Kim
Yongnam KIM
Deok Hwan Kim
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Assigned to LG CHEM, LTD. reassignment LG CHEM, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KIM, DEOK HWAN, KIM, JONG SEOK, KIM, Seiyong, KIM, Yongnam, PARK, SANG JUN
Publication of US20190280229A1 publication Critical patent/US20190280229A1/en
Application granted granted Critical
Publication of US11031566B2 publication Critical patent/US11031566B2/en
Active legal-status Critical Current
Adjusted expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H01L51/4213—
    • H01L51/42—
    • H01L51/44—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/86—Layers having high hole mobility, e.g. hole-transporting layers or electron-blocking layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present specification relates to a method for manufacturing a laminate for an organic-inorganic hybrid solar cell and a method for manufacturing an organic-inorganic hybrid solar cell.
  • the solar cell means a cell which produces current-voltage by using a photovoltaic effect of absorbing photoenergy from the sunlight to generate electrons and holes.
  • Organic-inorganic hybrid perovskite materials have recently drawn attention as a light absorbing material for organic-inorganic hybrid solar cells due to the characteristics in which the absorption coefficient is high and the material can be easily synthesized through a solution process.
  • a method for forming a top electrode of an organic-inorganic hybrid solar cell a method for depositing a metal material by a thermal deposition method or coating the metal material in the form of ink has been used.
  • these methods have problems in that the performance is changed according to the surface morphology of a bottom common layer and a metal oxide is formed, or an insulating layer in the form of an organic material/metal composite is formed when the bottom common layer is formed of an organic material.
  • the present specification provides a method for manufacturing a laminate for an organic-inorganic hybrid solar cell and a method for manufacturing an organic-inorganic hybrid solar cell, which have simple manufacturing processes.
  • An exemplary embodiment of the present specification provides a method for manufacturing a laminate for an organic-inorganic hybrid solar cell, the method including:
  • Another exemplary embodiment of the present specification provides a method for manufacturing an organic-inorganic hybrid solar cell, the method including:
  • a method for manufacturing a laminate for a solar cell it is possible to expect to shorten a process time and reduce process costs because an inexpensive metal ink can be applied, and a metal precursor sufficiently fills pores of an oxide common layer so that an effect of improving water vapor transmission characteristics is added, and as a result, an additional process for enhancing water vapor transmission characteristics is omitted.
  • the method for manufacturing a laminate for a solar cell prevents formation of an organic-metal composite and a metal oxide insulating layer which may be generated between a common layer material and an electrode layer material, thereby improving the efficiency of an organic-inorganic hybrid solar cell.
  • FIGS. 1 and 2 exemplify a structure of an organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification.
  • FIG. 3 illustrates a current density according to a voltage in each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
  • FIG. 4 illustrates scanning electron microscope (SEM) images of the cross-section of each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
  • FIG. 5 illustrates the water vapor transmission rate of each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
  • a method for manufacturing a laminate for an organic-inorganic hybrid solar cell includes: forming a metal precursor layer by using a metal precursor solution; and forming a common layer and an electrode by applying a metal hydride onto the metal precursor layer.
  • the common layer means an electron transporting layer or a hole transporting layer.
  • the laminate means a structure in which a common layer and an electrode are stacked.
  • the forming of the common layer and the electrode includes a procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode. That is, the forming of the common layer and the electrode includes a procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer becomes a common layer and the metal hydride becomes an electrode. At this time, the electrode is a metal electrode.
  • the procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode may be a procedure in which an oxide common layer is formed during the reduction of the metal hydride.
  • the forming of the metal precursor layer is carried out at 150° C. or less.
  • a metal precursor is treated at high temperature, and thus is applied to an oxide layer, and in this case, a material such as a substrate is thermally damaged, so that it is difficult to implement a device having high efficiency.
  • the present specification has effects in that a plastic base material, for example, a flexible substrate such as polyethylene terephthalate (PET) may be applied, and a device having high efficiency may be implemented by preventing materials from being thermally damaged because the forming of the metal precursor layer is carried out at 150° C. or less.
  • PET polyethylene terephthalate
  • an oxide precursor was used as a catalyst, the oxide precursor was not formed as an oxide layer, and finally, the prior art document failed to obtain effects of simultaneously improving processes of manufacturing a common layer and an electrode and improving the surface morphology of the common layer by using a system of placing an electrode manufactured of an aluminum film on an already manufactured common layer.
  • the method for manufacturing a laminate for an organic-inorganic hybrid solar cell includes a procedure in which a metal precursor layer is reacted with a metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode, and as a result, the common layer and the electrode are formed at one time, so that there is an effect in that the manufacturing process is simple and a device having high efficiency may be implemented.
  • the method for manufacturing a laminate for an organic-inorganic hybrid solar cell according to the present specification has an effect in that the surface morphology of the common layer is improved.
  • the metal precursor solution includes one or more metal precursors among a titanium (Ti) precursor, a zinc (Zn) precursor, an indium (In) precursor, a tin (Sn) precursor, a tungsten (W) precursor, a niobium (Nb) precursor, a molybdenum (Mo) precursor, a magnesium (Mg) precursor, a zirconium (Zr) precursor, a strontium (Sr) precursor, a lanthanum (La) precursor, a vanadium (V) precursor, an aluminum (Al) precursor, a yttrium (Y) precursor, a scandium (Sc) precursor, a samarium (Sm) precursor, a gallium (Ga) precursor, and a composite thereof.
  • a precursor means a material in a step before the material becomes a specific material in any metabolism or reaction.
  • a metal precursor means a material in a step before the material becomes a metal material
  • a metal precursor solution means a solution including a metal precursor.
  • the content of the metal precursor in the metal precursor solution is 0.1 wt % to 5 wt %. Specifically, the content is 1 wt % to 5 wt %.
  • the metal precursor solution includes a solvent.
  • a solvent it is possible to use a ketone solvent such as toluene and methyl ether ketone; an acetate solvent; an aldehyde-based solvent such as dimethyl formaldehyde; and an ether-based solvent, and the like. More specifically, since a bottom layer perovskite absorbing layer is vulnerable to an alcohol-based solvent, an ether-based solvent such as dimethyl ether and diethyl ether may be used.
  • a bottom layer perovskite absorbing layer means a light absorbing layer including a perovskite material provided at the bottom of a laminate.
  • the metal hydride includes a hydride of at least one metal among silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd).
  • the metal hydride may be an aluminum hydride.
  • a hydride means a two-element compound in which hydrogen combines with another element.
  • an aluminum hydride means that aluminum and hydrogen form a compound.
  • the metal precursor layer may be formed by a method such as spin coating, dip coating, spray coating, slit coating, and bar coating.
  • the forming of the common layer and the electrode by applying the metal hydride onto the metal precursor layer includes coating the metal hydride on the metal precursor layer by a method such as spin coating, dip coating, spray coating, slit coating, and bar coating.
  • a method for manufacturing an organic-inorganic hybrid solar cell includes:
  • forming an additional common layer may be further included between the forming of the first electrode and the forming of the light absorbing layer on the first electrode, and the common layer and the additional common layer may be each an electron transporting layer or a hole transporting layer.
  • the common layer may be an electron transporting layer and the additional common layer may be a hole transporting layer or the common layer may be a hole transporting layer and the additional common layer may be an electron transporting layer.
  • the method for manufacturing an organic-inorganic hybrid solar cell may include: sequentially forming a substrate, a first electrode, an electron transporting layer, a light absorbing layer, a hole transporting layer, and a second electrode.
  • FIG. 1 exemplifies a structure of an organic-inorganic hybrid solar cell manufactured according to an exemplary embodiment of the present specification. Specifically, FIG.
  • a first electrode 102 is provided on a substrate 101
  • an electron transporting layer 103 is provided on the first electrode 102
  • a light absorbing layer 104 is provided on the electron transporting layer 103
  • a hole transporting layer 105 is provided on the light absorbing layer 104
  • a second electrode 106 is provided on the hole transporting layer 105 .
  • the method for manufacturing an organic-inorganic hybrid solar cell may include: sequentially forming a substrate, a first electrode, a hole transporting layer, a light absorbing layer, an electron transporting layer, and a second electrode.
  • FIG. 2 exemplifies a structure of an organic-inorganic hybrid solar cell manufactured according to an exemplary embodiment of the present specification. Specifically, FIG.
  • a first electrode 102 is provided on a substrate 101
  • a hole transporting layer 105 is provided on the first electrode 102
  • a light absorbing layer 104 is provided on the hole transporting layer 105
  • an electron transporting layer 103 is provided on the light absorbing layer 104
  • a second electrode 106 is provided on the electron transporting layer 103 .
  • the common layer may have a thickness of 10 nm to 200 nm.
  • the forming of the light absorbing layer includes forming a perovskite material.
  • the perovskite material includes a structure of the following Chemical Formula 1.
  • AMX 3 [Chemical Formula 1]
  • A is a monovalent cation selected from C n H 2n+1 NH 3 + , NH 4+ , HC(NH 2 ) 2+ , Cs + , NF 4+ , NCl 4+ , PF 4+ , PCl 4 + , CH 3 PH 3+ , CH 3 AsH 3+ , CH 3 SbH 3+ , PH 4+ , AsH 4+ , and SbH 4+ ,
  • M is a divalent metal ion selected from Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Cr 2+ , Pd 2+ , Cd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , and Yb 2+ ,
  • X is a halogen ion
  • n is an integer from 1 to 9.
  • the perovskite material may be C n H 2n+1 NH 3 PbI 3 or HC(NH 2 ) 2 PbI 3 .
  • the perovskite material may be CH 3 NH 3 PbI 3 or HC(NH 2 ) 2 PbI 3 .
  • the substrate it is possible to use a substrate having excellent transparency, surface smoothness, handling easiness, and waterproofing property.
  • a glass substrate, a thin film glass substrate, or a plastic substrate may be used.
  • the plastic substrate may include a film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone, and polyimide in the form of a single layer or a multi-layer.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyether ether ketone polyimide
  • the substrate is not limited thereto, and a substrate typically used for an organic-inorganic hybrid solar cell may be used.
  • the first electrode may be an anode
  • the second electrode may be a cathode
  • the first electrode may be a cathode
  • the second electrode may be an anode
  • the first electrode may be a transparent electrode, and the solar cell may absorb light by way of the first electrode.
  • the electrode when the electrode is a transparent electrode, as the electrode, it is possible to use an electrode in which a material having conductivity is doped on a flexible and transparent material such as plastic including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), polycarbonate (PC), polystyrene (PS), polyoxyethylene (POE), an AS resin (acrylonitrile styrene copolymer), an ABS resin (acrylonitrile butadiene styrene copolymer), triacetyl cellulose (TAC), polyarylate (PAR), and the like, in addition to glass and a quartz plate.
  • plastic including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), polycarbonate (PC), polystyrene (PS), polyoxyethylene (POE), an AS resin (acrylonitrile styrene copolymer), an
  • the electrode may be indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), indium zinc oxide (IZO), ZnO—Ga 2 O 3 , ZnO—Al 2 O 3 , antimony tin oxide (ATO), and the like, and more specifically, ITO.
  • ITO indium tin oxide
  • FTO fluorine doped tin oxide
  • AZO aluminum doped zinc oxide
  • IZO indium zinc oxide
  • ZnO—Ga 2 O 3 ZnO—Al 2 O 3
  • antimony tin oxide (ATO) and the like, and more specifically, ITO.
  • the first electrode may be a semi-transparent electrode.
  • the first electrode may be manufactured of a semi-transparent metal such as silver (Ag), gold (Au), magnesium (Mg), or an alloy thereof.
  • a semi-transparent metal is used as a first electrode, the organic-inorganic hybrid solar cell may have a micro cavity structure.
  • the second electrode may be a metal electrode.
  • the metal electrode may include one or two or more selected from the group consisting of silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd).
  • the solar cell may further include an additional layer provided between the first electrode and the second electrode.
  • the additional layer may include one or more selected from the group consisting of a hole injection layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, and an electron injection layer.
  • a material for the hole transporting layer and/or the electron transporting layer may be a material which increases the probability that charges produced move to an electrode by efficiently transferring electrons and holes to a light absorbing layer, but is not particularly limited.
  • the electron transporting layer may include a metal oxide.
  • the metal oxide it is possible to specifically use one or two or more selected from Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, SrTi oxide, and a composite thereof, but the metal oxide is not limited thereto.
  • the electron transporting layer may improve characteristics of charges by using doping, and may modify a surface of the electron transporting layer by using a fluorene derivative, and the like.
  • the hole transporting layer may be an anode buffer layer.
  • the hole transporting layer may use tertiary butyl pyridine (TBP), lithium bis(trifluoro methanesulfonyl)imide (Li-TFSI), poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS), nickel oxide (NiOx), and the like, but the material is not limited thereto.
  • TBP tertiary butyl pyridine
  • Li-TFSI lithium bis(trifluoro methanesulfonyl)imide
  • PEDOT:PSS poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate)
  • NiOx nickel oxide
  • the light absorbing layer may be formed by a method such as spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, brush painting, and thermal deposition.
  • the organic-inorganic hybrid solar cell may have a wound structure.
  • the solar cell may be manufactured in the form of a flexible film, and may be made as a solar cell having a hollow wound structure by rolling the flexible film into a cylindrical form.
  • the solar cell has a wound structure, it is possible to install the solar cell in a way in which the solar cell is erected on the ground. In this case, it is possible to secure a portion in which the incident angle of light becomes a maximum while the sun moves from the east to the west at the position in which the solar cell is installed. Accordingly, while the sun is up in the sky, there is an advantage in that light may be absorbed as much as possible to increase the efficiency.
  • a glass substrate (40 ⁇ /sq) coated with indium tin oxide (ITO) was washed in ethanol for 20 minutes by using an ultrasonic wave.
  • An ITO substrate coated with an NiO x film (hereinafter, referred to as a hole transporting layer) was manufactured by spin-coating 2 wt % of a nickel oxide (NiO x ) dispersed solution (manufactured by Ditto, Inc.) on the aforementioned ITO substrate, and performing a heat treatment at 150° C. for 30 minutes.
  • a dimethylformamide (DMF) solution in which PbI 2 at a concentration of about 40 wt % was dissolved was spin-coated on the hole transporting layer. Thereafter, a light absorbing layer was formed by spin-coating an isopropyl alcohol (IPA) solution in which CH 3 NH 3 I (MAI) at a concentration of 4 wt % was dissolved, and then performing a heat treatment at 80° C. for 10 minutes.
  • IPA isopropyl alcohol
  • a metal precursor layer was formed by spin-coating dibutyl ether in which titanium tetrachloride (TiCl 4 ) at a concentration of 2 wt % was dissolved on the light absorbing layer, and then performing a heat treatment at 100° C. for 5 minutes.
  • TiCl 4 titanium tetrachloride
  • An electron transporting layer (TiO 2 ) was formed and an aluminum (Al) layer being a second electrode was formed on the electron transporting layer by dipping a film, in which a metal precursor layer for a hole transporting layer, a light absorbing layer, and an electron transporting layer was formed on the first electrode, in 50 mL of an aluminum precursor ink (manufactured by Alink Co., Ltd.) including a metal hydride for 1 hour, taking out the film, and performing a heat treatment at 100° C. for 30 minutes, thereby completing an organic-inorganic hybrid solar cell.
  • Al precursor ink manufactured by Alink Co., Ltd.
  • a glass substrate (40 ⁇ /sq) coated with indium tin oxide (ITO) was washed in ethanol for 20 minutes by using an ultrasonic wave.
  • An ITO substrate coated with an NiO x film (hereinafter, referred to as a hole transporting layer) was manufactured by spin-coating 2 wt % of a nickel oxide (NiO x ) dispersed solution (manufactured by Ditto, Inc.) on the aforementioned ITO substrate, and performing a heat treatment at 150° C. for 30 minutes.
  • a dimethylformamide (DMF) solution in which PbI 2 at a concentration of about 40 wt % was dissolved was spin-coated on the hole transporting layer. Thereafter, a light absorbing layer was formed by spin-coating an isopropyl alcohol (IPA) solution in which CH 3 NH 3 I (MAI) at a concentration of 4 wt % was dissolved, and then performing a heat treatment at 80° C. for 10 minutes.
  • IPA isopropyl alcohol
  • An electron transporting layer was formed by spin-coating a solution in which 2 wt % of titanium dioxide (TiO 2 ) particles were dispersed on the light absorbing layer, and performing a heat treatment at 100° C. for 30 minutes.
  • Aluminum (Al) was vacuum deposited to a thickness of about 120 nm to about 150 nm on the electron transporting layer under a pressure of 10 ⁇ 8 torr to form a second electrode, thereby completing an organic-inorganic hybrid solar cell.
  • Table 1 shows the performance of each of the organic-inorganic hybrid solar cells according to exemplary embodiments of the present specification
  • FIG. 3 illustrates a current density according to a voltage in each of the organic-inorganic hybrid solar cells manufactured in the exemplary embodiments of the present specification.
  • V oc , J sc , FF, and PCE mean an open-circuit voltage, a short-circuit current, a fill factor, and energy conversion efficiency, respectively.
  • the open-circuit voltage and the short-circuit current are an X axis intercept and a Y axis intercept, respectively, in the fourth quadrant of the voltage-current density curve, and as the two values are increased, the efficiency of the solar cell is preferably increased.
  • the fill factor is a value obtained by dividing the area of a rectangle, which may be drawn within the curve, by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency may be obtained when these three values are divided by the intensity of the irradiated light, and the higher value is preferred.
  • the organic-inorganic hybrid solar cell manufactured in the Example had an energy conversion efficiency value of about 12%, and exhibited a performance at a level equivalent to that of the organic-inorganic hybrid solar cell in the Comparative Example, in which the second electrode was formed by an existing vacuum deposition method.
  • FIG. 4 illustrates scanning electron microscope (SEM) images of the cross-section of each of organic-inorganic hybrid solar cells manufactured in the exemplary embodiments of the present specification.
  • SEM scanning electron microscope
  • FIG. 5 illustrates a result of measuring a water vapor transmission rate (WVTR) by forming an electron transporting layer and a second electrode laminate on a film in the same manner as the manufacturing method in the exemplary embodiments of the present specification.
  • WVTR water vapor transmission rate
  • the water vapor transmission rate of the laminate manufactured in the Comparative Example was about 4.87 g/m 2 day and exhibited a difference from 4.5 ⁇ 10 ⁇ 2 g/m 2 day, which was the water vapor transmission rate of the laminate manufactured in the Example, by about 1 ⁇ 10 ⁇ 2 g/m 2 day.
  • the laminate manufactured in the Example exhibited a water vapor transmission rate lower than that of the laminate manufactured in the Comparative Example.
  • the laminate manufactured by the solution process as in the Example may significantly increase the density as compared to a laminate made by a deposition process on the metal oxide common layer as in the Comparative Example.

Landscapes

  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

A method for manufacturing a laminate for an organic-inorganic hybrid solar cell, the method including forming a metal precursor layer by using a metal precursor solution, and forming a common layer and an electrode by applying a metal hydride onto the metal precursor layer.

Description

This application is a National Stage Application of International Application No. PCT/KR2017/007816 filed on Jul. 20, 2017, which claims priority to and the benefit of Korean Patent Application No. 10-2016-0093702 filed in the Korean Intellectual Property Office on Jul. 22, 2016, the entire contents of which are incorporated herein by reference in their entirety for all purposes as if fully set forth herein.
TECHNICAL FIELD
The present specification relates to a method for manufacturing a laminate for an organic-inorganic hybrid solar cell and a method for manufacturing an organic-inorganic hybrid solar cell.
BACKGROUND ART
In order to solve the global environmental problems caused by the depletion of fossil fuels and the use thereof, studies have been actively conducted on alternative energy sources, which may be regenerated and are clean, such as solar energy, wind power, and water power. Among them, interests in solar cells which change electric energy directly from the sunlight have been greatly increased. Here, the solar cell means a cell which produces current-voltage by using a photovoltaic effect of absorbing photoenergy from the sunlight to generate electrons and holes.
Organic-inorganic hybrid perovskite materials have recently drawn attention as a light absorbing material for organic-inorganic hybrid solar cells due to the characteristics in which the absorption coefficient is high and the material can be easily synthesized through a solution process.
In general, in the case of a process of an oxide applied to the manufacture of a common layer of an organic-inorganic hybrid solar cell, a method for treating a metal precursor at high temperature and applying the metal precursor to an oxide layer has been used. However, in this case, a process temperature at high temperature is needed, and it is difficult to implement a device having high efficiency. As another method, there is a method for coating and applying a solution in which metal oxide particles are prepared and dispersed, but in this case, the morphology of the common layer is non-uniform, so that it is difficult to apply a top electrode.
Meanwhile, as a method for forming a top electrode of an organic-inorganic hybrid solar cell, a method for depositing a metal material by a thermal deposition method or coating the metal material in the form of ink has been used. However, these methods have problems in that the performance is changed according to the surface morphology of a bottom common layer and a metal oxide is formed, or an insulating layer in the form of an organic material/metal composite is formed when the bottom common layer is formed of an organic material.
DETAILED DESCRIPTION OF THE INVENTION Technical Problem
The present specification provides a method for manufacturing a laminate for an organic-inorganic hybrid solar cell and a method for manufacturing an organic-inorganic hybrid solar cell, which have simple manufacturing processes.
Technical Solution
An exemplary embodiment of the present specification provides a method for manufacturing a laminate for an organic-inorganic hybrid solar cell, the method including:
forming a metal precursor layer by using a metal precursor solution; and
forming a common layer and an electrode by applying a metal hydride onto the metal precursor layer.
Further, another exemplary embodiment of the present specification provides a method for manufacturing an organic-inorganic hybrid solar cell, the method including:
forming a first electrode;
forming a light absorbing layer on the first electrode;
forming a metal precursor layer on the light absorbing layer by using a metal precursor solution; and
forming a common layer and a second electrode by applying a metal hydride onto the metal precursor layer.
Advantageous Effects
According to a method for manufacturing a laminate for a solar cell according to an exemplary embodiment of the present specification, it is possible to expect to shorten a process time and reduce process costs because an inexpensive metal ink can be applied, and a metal precursor sufficiently fills pores of an oxide common layer so that an effect of improving water vapor transmission characteristics is added, and as a result, an additional process for enhancing water vapor transmission characteristics is omitted.
The method for manufacturing a laminate for a solar cell according to an exemplary embodiment of the present specification prevents formation of an organic-metal composite and a metal oxide insulating layer which may be generated between a common layer material and an electrode layer material, thereby improving the efficiency of an organic-inorganic hybrid solar cell.
BRIEF DESCRIPTION OF DRAWINGS
FIGS. 1 and 2 exemplify a structure of an organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification.
FIG. 3 illustrates a current density according to a voltage in each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
FIG. 4 illustrates scanning electron microscope (SEM) images of the cross-section of each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
FIG. 5 illustrates the water vapor transmission rate of each of the organic-inorganic hybrid solar cells manufactured in exemplary embodiments of the present specification.
    • 101: Substrate
    • 102: First electrode
    • 103: Electron transporting layer
    • 104: Light absorbing layer
    • 105: Hole transporting layer
    • 106: Second electrode
BEST MODE
Hereinafter, the present specification will be described in detail.
When one part “includes” one constituent element in the present specification, unless otherwise specifically described, this does not mean that another constituent element is excluded, but means that another constituent element may be further included.
When one member is disposed “on” another member in the present specification, this includes not only a case where the one member is brought into contact with another member, but also a case where still another member is present between the two members.
A method for manufacturing a laminate for an organic-inorganic hybrid solar cell according to an exemplary embodiment of the present specification includes: forming a metal precursor layer by using a metal precursor solution; and forming a common layer and an electrode by applying a metal hydride onto the metal precursor layer.
In the present specification, the common layer means an electron transporting layer or a hole transporting layer.
In the present specification, the laminate means a structure in which a common layer and an electrode are stacked.
According to an exemplary embodiment of the present specification, the forming of the common layer and the electrode includes a procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode. That is, the forming of the common layer and the electrode includes a procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer becomes a common layer and the metal hydride becomes an electrode. At this time, the electrode is a metal electrode.
In the present specification, the procedure in which the metal precursor layer is reacted with the metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode may be a procedure in which an oxide common layer is formed during the reduction of the metal hydride.
In the present specification, the forming of the metal precursor layer is carried out at 150° C. or less. In general, in the case of an oxide process applied to the manufacture of the common layer, a metal precursor is treated at high temperature, and thus is applied to an oxide layer, and in this case, a material such as a substrate is thermally damaged, so that it is difficult to implement a device having high efficiency. The present specification has effects in that a plastic base material, for example, a flexible substrate such as polyethylene terephthalate (PET) may be applied, and a device having high efficiency may be implemented by preventing materials from being thermally damaged because the forming of the metal precursor layer is carried out at 150° C. or less.
In general, in order to form an electrode, a method such as thermal deposition, sputter coating, and vacuum deposition has been used, and in this case, there are problems in that a large amount of raw materials are lost, a lot of costs are consumed in order to manufacture and maintain facilities, and it is difficult to maintain process conditions. As a method for solving the problems, a prior art document (Korean Patent No. 10-1144246) describes that an electrode is formed by preparing an aluminum precursor ink in a metal precursor for a wet process. However, in the prior art document, an oxide precursor was used as a catalyst, the oxide precursor was not formed as an oxide layer, and finally, the prior art document failed to obtain effects of simultaneously improving processes of manufacturing a common layer and an electrode and improving the surface morphology of the common layer by using a system of placing an electrode manufactured of an aluminum film on an already manufactured common layer.
The method for manufacturing a laminate for an organic-inorganic hybrid solar cell according to the present specification includes a procedure in which a metal precursor layer is reacted with a metal hydride, so that the metal precursor layer is formed as a common layer and the metal hydride is formed as an electrode, and as a result, the common layer and the electrode are formed at one time, so that there is an effect in that the manufacturing process is simple and a device having high efficiency may be implemented.
Further, the method for manufacturing a laminate for an organic-inorganic hybrid solar cell according to the present specification has an effect in that the surface morphology of the common layer is improved.
In the present specification, the metal precursor solution includes one or more metal precursors among a titanium (Ti) precursor, a zinc (Zn) precursor, an indium (In) precursor, a tin (Sn) precursor, a tungsten (W) precursor, a niobium (Nb) precursor, a molybdenum (Mo) precursor, a magnesium (Mg) precursor, a zirconium (Zr) precursor, a strontium (Sr) precursor, a lanthanum (La) precursor, a vanadium (V) precursor, an aluminum (Al) precursor, a yttrium (Y) precursor, a scandium (Sc) precursor, a samarium (Sm) precursor, a gallium (Ga) precursor, and a composite thereof.
In the present specification, a precursor means a material in a step before the material becomes a specific material in any metabolism or reaction. For example, a metal precursor means a material in a step before the material becomes a metal material, and a metal precursor solution means a solution including a metal precursor.
According to an exemplary embodiment of the present specification, the content of the metal precursor in the metal precursor solution is 0.1 wt % to 5 wt %. Specifically, the content is 1 wt % to 5 wt %.
In the present specification, the metal precursor solution includes a solvent. Specifically, as the solvent, it is possible to use a ketone solvent such as toluene and methyl ether ketone; an acetate solvent; an aldehyde-based solvent such as dimethyl formaldehyde; and an ether-based solvent, and the like. More specifically, since a bottom layer perovskite absorbing layer is vulnerable to an alcohol-based solvent, an ether-based solvent such as dimethyl ether and diethyl ether may be used.
In the present specification, a bottom layer perovskite absorbing layer means a light absorbing layer including a perovskite material provided at the bottom of a laminate.
According to an exemplary embodiment of the present specification, the metal hydride includes a hydride of at least one metal among silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd). For example, the metal hydride may be an aluminum hydride.
In the present specification, a hydride means a two-element compound in which hydrogen combines with another element. For example, an aluminum hydride means that aluminum and hydrogen form a compound.
In the present specification, the metal precursor layer may be formed by a method such as spin coating, dip coating, spray coating, slit coating, and bar coating.
In the present specification, the forming of the common layer and the electrode by applying the metal hydride onto the metal precursor layer includes coating the metal hydride on the metal precursor layer by a method such as spin coating, dip coating, spray coating, slit coating, and bar coating.
According to an exemplary embodiment of the present specification, a method for manufacturing an organic-inorganic hybrid solar cell includes:
forming a first electrode;
forming a light absorbing layer on the first electrode;
forming a metal precursor layer on the light absorbing layer by using a metal precursor solution; and
forming a common layer and a second electrode by applying a metal hydride onto the metal precursor layer.
At this time, forming an additional common layer may be further included between the forming of the first electrode and the forming of the light absorbing layer on the first electrode, and the common layer and the additional common layer may be each an electron transporting layer or a hole transporting layer. For example, the common layer may be an electron transporting layer and the additional common layer may be a hole transporting layer or the common layer may be a hole transporting layer and the additional common layer may be an electron transporting layer.
For example, in the present specification, the method for manufacturing an organic-inorganic hybrid solar cell may include: sequentially forming a substrate, a first electrode, an electron transporting layer, a light absorbing layer, a hole transporting layer, and a second electrode. FIG. 1 exemplifies a structure of an organic-inorganic hybrid solar cell manufactured according to an exemplary embodiment of the present specification. Specifically, FIG. 1 exemplifies a structure of an organic-inorganic hybrid solar cell, in which a first electrode 102 is provided on a substrate 101, an electron transporting layer 103 is provided on the first electrode 102, a light absorbing layer 104 is provided on the electron transporting layer 103, a hole transporting layer 105 is provided on the light absorbing layer 104, and a second electrode 106 is provided on the hole transporting layer 105.
For another example, the method for manufacturing an organic-inorganic hybrid solar cell may include: sequentially forming a substrate, a first electrode, a hole transporting layer, a light absorbing layer, an electron transporting layer, and a second electrode. FIG. 2 exemplifies a structure of an organic-inorganic hybrid solar cell manufactured according to an exemplary embodiment of the present specification. Specifically, FIG. 2 exemplifies a structure of an organic-inorganic hybrid solar cell, in which a first electrode 102 is provided on a substrate 101, a hole transporting layer 105 is provided on the first electrode 102, a light absorbing layer 104 is provided on the hole transporting layer 105, an electron transporting layer 103 is provided on the light absorbing layer 104, and a second electrode 106 is provided on the electron transporting layer 103.
In the present specification, the common layer may have a thickness of 10 nm to 200 nm.
According to an exemplary embodiment of the present specification, the forming of the light absorbing layer includes forming a perovskite material.
In the present specification, the perovskite material includes a structure of the following Chemical Formula 1.
AMX3  [Chemical Formula 1]
In Chemical Formula 1,
A is a monovalent cation selected from CnH2n+1NH3 +, NH4+, HC(NH2)2+, Cs+, NF4+, NCl4+, PF4+, PCl4 +, CH3PH3+, CH3AsH3+, CH3SbH3+, PH4+, AsH4+, and SbH4+,
M is a divalent metal ion selected from Cu2+, Ni2+, Co2+, Fe2+, Mn2+, Cr2+, Pd2+, Cd2+, Ge2+, Sn2+, Pb2+, and Yb2+,
X is a halogen ion, and
n is an integer from 1 to 9.
For example, the perovskite material may be CnH2n+1NH3PbI3 or HC(NH2)2PbI3. For example, the perovskite material may be CH3NH3PbI3 or HC(NH2)2PbI3.
In the present specification, as the substrate, it is possible to use a substrate having excellent transparency, surface smoothness, handling easiness, and waterproofing property. Specifically, a glass substrate, a thin film glass substrate, or a plastic substrate may be used. The plastic substrate may include a film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether ether ketone, and polyimide in the form of a single layer or a multi-layer. However, the substrate is not limited thereto, and a substrate typically used for an organic-inorganic hybrid solar cell may be used.
In the present specification, the first electrode may be an anode, and the second electrode may be a cathode. Further, the first electrode may be a cathode, and the second electrode may be an anode.
In the present specification, the first electrode may be a transparent electrode, and the solar cell may absorb light by way of the first electrode.
In the present specification, when the electrode is a transparent electrode, as the electrode, it is possible to use an electrode in which a material having conductivity is doped on a flexible and transparent material such as plastic including polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), polycarbonate (PC), polystyrene (PS), polyoxyethylene (POE), an AS resin (acrylonitrile styrene copolymer), an ABS resin (acrylonitrile butadiene styrene copolymer), triacetyl cellulose (TAC), polyarylate (PAR), and the like, in addition to glass and a quartz plate.
Specifically, the electrode may be indium tin oxide (ITO), fluorine doped tin oxide (FTO), aluminum doped zinc oxide (AZO), indium zinc oxide (IZO), ZnO—Ga2O3, ZnO—Al2O3, antimony tin oxide (ATO), and the like, and more specifically, ITO.
Furthermore, the first electrode may be a semi-transparent electrode. When the first electrode is a semi-transparent electrode, the first electrode may be manufactured of a semi-transparent metal such as silver (Ag), gold (Au), magnesium (Mg), or an alloy thereof. When a semi-transparent metal is used as a first electrode, the organic-inorganic hybrid solar cell may have a micro cavity structure.
In the present specification, the second electrode may be a metal electrode. Specifically, the metal electrode may include one or two or more selected from the group consisting of silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd).
In the present specification, the solar cell may further include an additional layer provided between the first electrode and the second electrode. Specifically, according to an exemplary embodiment of the present specification, the additional layer may include one or more selected from the group consisting of a hole injection layer, a hole transporting layer, an electron blocking layer, an electron transporting layer, and an electron injection layer.
In the present specification, a material for the hole transporting layer and/or the electron transporting layer may be a material which increases the probability that charges produced move to an electrode by efficiently transferring electrons and holes to a light absorbing layer, but is not particularly limited.
In the present specification, the electron transporting layer may include a metal oxide. As the metal oxide, it is possible to specifically use one or two or more selected from Ti oxide, Zn oxide, In oxide, Sn oxide, W oxide, Nb oxide, Mo oxide, Mg oxide, Zr oxide, Sr oxide, Yr oxide, La oxide, V oxide, Al oxide, Y oxide, Sc oxide, Sm oxide, Ga oxide, SrTi oxide, and a composite thereof, but the metal oxide is not limited thereto.
In the present specification, the electron transporting layer may improve characteristics of charges by using doping, and may modify a surface of the electron transporting layer by using a fluorene derivative, and the like.
In the present specification, the hole transporting layer may be an anode buffer layer.
The hole transporting layer may use tertiary butyl pyridine (TBP), lithium bis(trifluoro methanesulfonyl)imide (Li-TFSI), poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS), nickel oxide (NiOx), and the like, but the material is not limited thereto.
In the present specification, the light absorbing layer may be formed by a method such as spin coating, slit coating, dip coating, inkjet printing, gravure printing, spray coating, doctor blade, bar coating, brush painting, and thermal deposition.
In the present specification, the organic-inorganic hybrid solar cell may have a wound structure. Specifically, the solar cell may be manufactured in the form of a flexible film, and may be made as a solar cell having a hollow wound structure by rolling the flexible film into a cylindrical form. When the solar cell has a wound structure, it is possible to install the solar cell in a way in which the solar cell is erected on the ground. In this case, it is possible to secure a portion in which the incident angle of light becomes a maximum while the sun moves from the east to the west at the position in which the solar cell is installed. Accordingly, while the sun is up in the sky, there is an advantage in that light may be absorbed as much as possible to increase the efficiency.
MODE FOR INVENTION
Hereinafter, the present specification will be described in detail with reference to Examples for specifically describing the present specification. However, the Examples according to the present specification may be modified in various forms, and it is not interpreted that the scope of the present specification is limited to the Examples described below in detail. The Examples of the present specification are provided to more completely explain the present specification to a person with ordinary skill in the art.
Example
A glass substrate (40 Ω/sq) coated with indium tin oxide (ITO) was washed in ethanol for 20 minutes by using an ultrasonic wave. An ITO substrate coated with an NiOx film (hereinafter, referred to as a hole transporting layer) was manufactured by spin-coating 2 wt % of a nickel oxide (NiOx) dispersed solution (manufactured by Ditto, Inc.) on the aforementioned ITO substrate, and performing a heat treatment at 150° C. for 30 minutes.
In order to form a light absorbing layer, a dimethylformamide (DMF) solution in which PbI2 at a concentration of about 40 wt % was dissolved was spin-coated on the hole transporting layer. Thereafter, a light absorbing layer was formed by spin-coating an isopropyl alcohol (IPA) solution in which CH3NH3I (MAI) at a concentration of 4 wt % was dissolved, and then performing a heat treatment at 80° C. for 10 minutes.
A metal precursor layer was formed by spin-coating dibutyl ether in which titanium tetrachloride (TiCl4) at a concentration of 2 wt % was dissolved on the light absorbing layer, and then performing a heat treatment at 100° C. for 5 minutes.
An electron transporting layer (TiO2) was formed and an aluminum (Al) layer being a second electrode was formed on the electron transporting layer by dipping a film, in which a metal precursor layer for a hole transporting layer, a light absorbing layer, and an electron transporting layer was formed on the first electrode, in 50 mL of an aluminum precursor ink (manufactured by Alink Co., Ltd.) including a metal hydride for 1 hour, taking out the film, and performing a heat treatment at 100° C. for 30 minutes, thereby completing an organic-inorganic hybrid solar cell.
Comparative Example
A glass substrate (40 Ω/sq) coated with indium tin oxide (ITO) was washed in ethanol for 20 minutes by using an ultrasonic wave. An ITO substrate coated with an NiOx film (hereinafter, referred to as a hole transporting layer) was manufactured by spin-coating 2 wt % of a nickel oxide (NiOx) dispersed solution (manufactured by Ditto, Inc.) on the aforementioned ITO substrate, and performing a heat treatment at 150° C. for 30 minutes.
In order to form a light absorbing layer, a dimethylformamide (DMF) solution in which PbI2 at a concentration of about 40 wt % was dissolved was spin-coated on the hole transporting layer. Thereafter, a light absorbing layer was formed by spin-coating an isopropyl alcohol (IPA) solution in which CH3NH3I (MAI) at a concentration of 4 wt % was dissolved, and then performing a heat treatment at 80° C. for 10 minutes.
An electron transporting layer was formed by spin-coating a solution in which 2 wt % of titanium dioxide (TiO2) particles were dispersed on the light absorbing layer, and performing a heat treatment at 100° C. for 30 minutes.
Aluminum (Al) was vacuum deposited to a thickness of about 120 nm to about 150 nm on the electron transporting layer under a pressure of 10−8 torr to form a second electrode, thereby completing an organic-inorganic hybrid solar cell.
Table 1 shows the performance of each of the organic-inorganic hybrid solar cells according to exemplary embodiments of the present specification, and FIG. 3 illustrates a current density according to a voltage in each of the organic-inorganic hybrid solar cells manufactured in the exemplary embodiments of the present specification.
TABLE 1
PCE (%) Jsc (mA/cm2) Voc (V) FF (%)
Example 12.0 19.6 0.941 65.1
Comparative Example 12.5 19.7 0.961 66.1
In Table 1, Voc, Jsc, FF, and PCE mean an open-circuit voltage, a short-circuit current, a fill factor, and energy conversion efficiency, respectively. The open-circuit voltage and the short-circuit current are an X axis intercept and a Y axis intercept, respectively, in the fourth quadrant of the voltage-current density curve, and as the two values are increased, the efficiency of the solar cell is preferably increased. In addition, the fill factor is a value obtained by dividing the area of a rectangle, which may be drawn within the curve, by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency may be obtained when these three values are divided by the intensity of the irradiated light, and the higher value is preferred.
The organic-inorganic hybrid solar cell manufactured in the Example had an energy conversion efficiency value of about 12%, and exhibited a performance at a level equivalent to that of the organic-inorganic hybrid solar cell in the Comparative Example, in which the second electrode was formed by an existing vacuum deposition method.
FIG. 4 illustrates scanning electron microscope (SEM) images of the cross-section of each of organic-inorganic hybrid solar cells manufactured in the exemplary embodiments of the present specification. In the case of the device manufactured in the Comparative Example, an interface between the aluminum thin film being the second electrode and the electron transporting layer thin film was noticeable, and a lifting interval confirmed as pores was exhibited, whereas in the case of the device manufactured in the Example, the aluminum thin film being the second electrode and the electron transporting layer thin film were too entangled with each other to differentiate the interface between the two thin films, and pores between the two layers were not confirmed.
FIG. 5 illustrates a result of measuring a water vapor transmission rate (WVTR) by forming an electron transporting layer and a second electrode laminate on a film in the same manner as the manufacturing method in the exemplary embodiments of the present specification. At this time, the water vapor transmission rate was measured by using an AQUATRAN-2 water vapor transmission rate measurement device manufactured by MOCON, Inc. The water vapor transmission rate of the laminate manufactured in the Comparative Example was about 4.87 g/m2 day and exhibited a difference from 4.5×10−2 g/m2 day, which was the water vapor transmission rate of the laminate manufactured in the Example, by about 1×10−2 g/m2 day. That is, the laminate manufactured in the Example exhibited a water vapor transmission rate lower than that of the laminate manufactured in the Comparative Example. Through the results, it can be seen that the laminate manufactured by the solution process as in the Example may significantly increase the density as compared to a laminate made by a deposition process on the metal oxide common layer as in the Comparative Example.

Claims (12)

The invention claimed is:
1. A method for manufacturing a laminate for an organic-inorganic hybrid solar cell, the method comprising:
forming a metal precursor layer by using a metal precursor solution; and
forming a common layer and an electrode by applying a metal hydride to the metal precursor layer.
2. The method for manufacturing a laminate for an organic-inorganic hybrid solar cell of claim 1, further comprising reacting the metal precursor layer with the metal hydride, so that the metal precursor layer becomes the common layer, and the metal hydride becomes the electrode.
3. The method for manufacturing a laminate for an organic-inorganic hybrid solar cell of claim 1, wherein the metal precursor solution includes one or more metal precursors selected from the group consisting of a: titanium (Ti) precursor, a zinc (Zn) precursor, an indium (In) precursor, a tin (Sn) precursor, a tungsten (W) precursor, a niobium (Nb) precursor, a molybdenum (Mo) precursor, a magnesium (Mg) precursor, a zirconium (Zr) precursor, a strontium (Sr) precursor, a lanthanum (La) precursor, a vanadium (V) precursor, an aluminum (Al) precursor, a yttrium (Y) precursor, a scandium (Sc) precursor, a samarium (Sm) precursor, a gallium (Ga) precursor, and a composite thereof.
4. The method for manufacturing a laminate for an organic-inorganic hybrid solar cell of claim 1, wherein a content of the metal precursor in the metal precursor solution is 0.1 wt % to 5 wt %.
5. The method for manufacturing a laminate for an organic-inorganic hybrid solar cell of claim 1, the metal precursor layer is formed at 150° C. or less.
6. The method for manufacturing a laminate for an organic-inorganic hybrid solar cell of claim 1, wherein the metal hydride includes a hydride of at least one metal selected from the group consisting of: silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), and palladium (Pd).
7. A method for manufacturing an organic-inorganic hybrid solar cell, the method comprising:
forming a first electrode;
forming a light absorbing layer on the first electrode;
forming a metal precursor layer on the light absorbing layer by using a metal precursor solution; and
forming a common layer and a second electrode by applying a metal hydride to the metal precursor layer.
8. The method for manufacturing an organic-inorganic hybrid solar cell of claim 7, further comprising:
forming an additional common layer after forming the first electrode and before forming the light absorbing layer on the first electrode.
9. The method for manufacturing an organic-inorganic hybrid solar cell of claim 7, wherein the common layer is an electron transporting layer or a hole transporting layer.
10. The method for manufacturing an organic-inorganic hybrid solar cell of claim 8, wherein the common layer is an electron transporting layer and the additional common layer is a hole transporting layer, or the common layer is a hole transporting layer and the additional common layer is an electron transporting layer.
11. The method for manufacturing an organic-inorganic hybrid solar cell of claim 7, wherein forming the light absorbing layer comprises forming a perovskite material.
12. The method for manufacturing an organic-inorganic hybrid solar cell of claim 7, wherein the common layer has a thickness of 10 nm to 200 nm.
US16/319,236 2016-07-22 2017-07-20 Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell Active 2038-07-29 US11031566B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR10-2016-0093702 2016-07-22
KR1020160093702A KR102072884B1 (en) 2016-07-22 2016-07-22 Method of manufacturing laminate for organic-inorganic complex solar cell, and method for manufacturing organic-inorganic complex solar cell
PCT/KR2017/007816 WO2018016886A1 (en) 2016-07-22 2017-07-20 Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell

Publications (2)

Publication Number Publication Date
US20190280229A1 US20190280229A1 (en) 2019-09-12
US11031566B2 true US11031566B2 (en) 2021-06-08

Family

ID=60992333

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/319,236 Active 2038-07-29 US11031566B2 (en) 2016-07-22 2017-07-20 Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell

Country Status (5)

Country Link
US (1) US11031566B2 (en)
JP (1) JP6783998B2 (en)
KR (1) KR102072884B1 (en)
CN (1) CN109478597B (en)
WO (1) WO2018016886A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102182519B1 (en) * 2019-03-18 2020-11-24 에이치디씨아이콘트롤스 주식회사 SnS Film Manufacturing Method, SnS Film, and Photovoltaic Device Using It
SE543601C2 (en) 2019-10-23 2021-04-13 Anesteasy Ab Intravascular catheter device
KR102658357B1 (en) * 2021-12-28 2024-04-18 주식회사 메카로에너지 Perovskite solar cell with energy conversion efficiency

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070184576A1 (en) 2005-11-29 2007-08-09 Oregon State University Solution deposition of inorganic materials and electronic devices made comprising the inorganic materials
US20080283389A1 (en) 2004-05-11 2008-11-20 Honda Motor Co., Ltd. Method for Manufacturing Chalcopyrite Thin-Film Solar Cell
JP2010161270A (en) 2009-01-09 2010-07-22 Konica Minolta Holdings Inc Organic photoelectric conversion element and manufacturing method therefor
KR100991005B1 (en) 2008-08-29 2010-10-29 고려대학교 산학협력단 Electrode formation based on photo-induced reduction of metal ions in the presence of metal nanomaterials
KR101021280B1 (en) 2010-11-11 2011-03-11 한국기계연구원 The preparing method for aluminum cathode using wetting process and the aluminum cathode thereby
US20110284068A1 (en) 2010-04-23 2011-11-24 Solexel, Inc. Passivation methods and apparatus for achieving ultra-low surface recombination velocities for high-efficiency solar cells
KR101144246B1 (en) 2012-01-02 2012-05-10 한국기계연구원 Aluminum precursor ink for wet process and the preparation method thereof
KR101345101B1 (en) 2012-12-10 2013-12-26 한국기계연구원 Method for manufacturing conductive metal thin layer, electrode thereby, organic optoelectronic device, battery and solar cell including the electrode
KR101373787B1 (en) 2011-01-12 2014-03-17 지에스칼텍스 주식회사 Method of manufacturing thin film solar cell using alkali hydride
US20140144501A1 (en) 2012-11-26 2014-05-29 Electronics And Telecommunications Research Institute Method of fabricating a transparent electrode and a dye-sensitized solar cell using the transparent electrode
WO2014119943A1 (en) 2013-01-31 2014-08-07 포항공과대학교 산학협력단 Method for fabricating large metal nanofiber electrode array using aligned metal nanofiber
KR20150106858A (en) 2014-03-12 2015-09-22 한국화학연구원 Mixed Metal Halide Perovskite Compound and the Semiconductor Device having Thereof
US20150279573A1 (en) 2014-03-27 2015-10-01 Ricoh Company, Ltd. Perovskite solar cell
US20150287848A1 (en) 2013-06-17 2015-10-08 Young-Kwon Jun Solar cell and method of manufacturing therefor
US20160268510A1 (en) 2015-03-12 2016-09-15 Korea Research Institute Of Chemical Technology Mixed metal halide perovskite compound and semiconductor device including the same
KR101662885B1 (en) 2014-03-17 2016-10-07 전영권 Solar cells and manufacturing method for the same
US20170077403A1 (en) 2013-01-31 2017-03-16 Postech Academy- Industry Foundation Method for fabricating large metal nanofiber electrode array using aligned metal nanofiber

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4076749B2 (en) * 2001-10-15 2008-04-16 富士フイルム株式会社 Conductive organic compound and electronic device
JP3817201B2 (en) * 2002-04-19 2006-09-06 Ｊｓｒ株式会社 Conductive film forming composition, conductive film and method for forming the same
KR100765684B1 (en) * 2002-07-03 2007-10-11 삼성전자주식회사 Organometallic Precursors for Forming Metal Alloy Pattern and Method for Forming Metal Alloy Pattern Using The Same
EP1842854A1 (en) * 2006-04-07 2007-10-10 SOLVAY (Société Anonyme) Light-emitting material
KR20110046439A (en) * 2008-07-24 2011-05-04 코비오 인코포레이티드 Aluminum ink and its manufacturing method, aluminum ink deposition method and film formed by printing and / or deposition of aluminum ink
CN102792508A (en) * 2010-01-19 2012-11-21 双向电池公司 Low-cost, high power, high energy density, solid-state, bipolar metal hydride batteries
EP2766911B1 (en) * 2011-10-11 2019-02-13 Exeger Sweden AB Method for manufacturing dye-sensitized solar cells and solar cells so produced
CN102911554A (en) * 2012-10-22 2013-02-06 中国科学院苏州纳米技术与纳米仿生研究所 Organic aluminum ink and aluminum electrode preparation method

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080283389A1 (en) 2004-05-11 2008-11-20 Honda Motor Co., Ltd. Method for Manufacturing Chalcopyrite Thin-Film Solar Cell
US20070184576A1 (en) 2005-11-29 2007-08-09 Oregon State University Solution deposition of inorganic materials and electronic devices made comprising the inorganic materials
US8268536B2 (en) 2008-08-29 2012-09-18 Korea University Research And Business Foundation Electrode formation based on photo-induced reduction of metal ions in the presence of metal nanomaterials
KR100991005B1 (en) 2008-08-29 2010-10-29 고려대학교 산학협력단 Electrode formation based on photo-induced reduction of metal ions in the presence of metal nanomaterials
JP2010161270A (en) 2009-01-09 2010-07-22 Konica Minolta Holdings Inc Organic photoelectric conversion element and manufacturing method therefor
US20110284068A1 (en) 2010-04-23 2011-11-24 Solexel, Inc. Passivation methods and apparatus for achieving ultra-low surface recombination velocities for high-efficiency solar cells
US20130213690A1 (en) 2010-11-11 2013-08-22 Korea Institute Of Machinery And Materials Method for manufacturing aluminum electrode using solution process and aluminum electrode manufactures thereby
KR101021280B1 (en) 2010-11-11 2011-03-11 한국기계연구원 The preparing method for aluminum cathode using wetting process and the aluminum cathode thereby
KR101373787B1 (en) 2011-01-12 2014-03-17 지에스칼텍스 주식회사 Method of manufacturing thin film solar cell using alkali hydride
KR101144246B1 (en) 2012-01-02 2012-05-10 한국기계연구원 Aluminum precursor ink for wet process and the preparation method thereof
US20140144501A1 (en) 2012-11-26 2014-05-29 Electronics And Telecommunications Research Institute Method of fabricating a transparent electrode and a dye-sensitized solar cell using the transparent electrode
KR101345101B1 (en) 2012-12-10 2013-12-26 한국기계연구원 Method for manufacturing conductive metal thin layer, electrode thereby, organic optoelectronic device, battery and solar cell including the electrode
WO2014119943A1 (en) 2013-01-31 2014-08-07 포항공과대학교 산학협력단 Method for fabricating large metal nanofiber electrode array using aligned metal nanofiber
US20170077403A1 (en) 2013-01-31 2017-03-16 Postech Academy- Industry Foundation Method for fabricating large metal nanofiber electrode array using aligned metal nanofiber
US20150287848A1 (en) 2013-06-17 2015-10-08 Young-Kwon Jun Solar cell and method of manufacturing therefor
KR20150106858A (en) 2014-03-12 2015-09-22 한국화학연구원 Mixed Metal Halide Perovskite Compound and the Semiconductor Device having Thereof
KR101662885B1 (en) 2014-03-17 2016-10-07 전영권 Solar cells and manufacturing method for the same
US20150279573A1 (en) 2014-03-27 2015-10-01 Ricoh Company, Ltd. Perovskite solar cell
US20160268510A1 (en) 2015-03-12 2016-09-15 Korea Research Institute Of Chemical Technology Mixed metal halide perovskite compound and semiconductor device including the same

Also Published As

Publication number Publication date
KR102072884B1 (en) 2020-02-03
KR20180010874A (en) 2018-01-31
JP6783998B2 (en) 2020-11-11
CN109478597B (en) 2022-07-19
US20190280229A1 (en) 2019-09-12
CN109478597A (en) 2019-03-15
WO2018016886A1 (en) 2018-01-25
JP2019521524A (en) 2019-07-25

Similar Documents

Publication Publication Date Title
EP3172776B9 (en) Mesoscopic framework for organic-inorganic perovskite based photoelectric conversion device and method for manufacturing the same
EP3306691B1 (en) Organic-inorganic composite solar cell
EP3392915A1 (en) Monolithic-type module of perovskite solar cell, and manufacturing method therefor
US20190180946A1 (en) Organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell
JP2009088045A (en) Photoelectric converting element and its manufacturing method
US11031566B2 (en) Method for manufacturing laminate for organic-inorganic hybrid solar cell and method for manufacturing organic-inorganic hybrid solar cell
WO2016023064A1 (en) A photovoltaic cell and a method of forming a photovoltaic cell
KR101694803B1 (en) Perovskite solar cells comprising metal nanowire as photoelectrode, and the preparation method thereof
US11004617B2 (en) Method for manufacturing organic-inorganic hybrid solar cell
US11177078B2 (en) Light-absorbing layer precursor, organic-inorganic hybrid solar cell manufacturing method using same, and organic-inorganic hybrid solar cell
KR102201896B1 (en) Massive Fabrication Method of Perovskite Solar Cell
CN112599681A (en) Perovskite solar cell with improved metal electrode and preparation method thereof
KR20170132567A (en) Method of manufacturing the optical absorber layer for organic-inorganic complex solar cell, and method of manufacturing organic-inorganic complex solar cell using thereof
KR20170051169A (en) Charge collection layer of perovskite solar cell by using electro-spray deposition and manufacturing method thereof
EP3428988B1 (en) Organic-inorganic hybrid solar cell
KR101714750B1 (en) Control method for morphology of metal oxide film
CN115915777A (en) Preparation method of perovskite device

Legal Events

Date Code Title Description
AS Assignment

Owner name: LG CHEM, LTD., KOREA, REPUBLIC OF

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:PARK, SANG JUN;KIM, SEIYONG;KIM, JONG SEOK;AND OTHERS;REEL/FRAME:048063/0232

Effective date: 20170719

FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT RECEIVED

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE